Stabilization of coloring compositions containing diazonium salts



memes June 12, 1945 UNITED-1 STATE s- Partition-ice STABILIZATION FCOLORING COMPOSI- TION S CONTAINING'DIAZONIUM SALTS Hans Z. Lecher,Plainfleld, and William B. Hardy and Frederic B. Adams, Bound Brook, N.J., assignors'to American Cyanamid Company, New York, N. Y., acorporation of Maine No Drawing. Application July 5, I943, I Serial No.493,594

13 Claims.

An important method of producing prints of azoic colors on vegetablefibers consists in pad ding the goods with an alkaline solution of an'azoic coupling component and printing these goods with sprinting pastecontaining a dimnium salt derived from an ice color diazocom I ponent.The diazoniuin salt is either prepared by the printer himself bydiazotizing the corresponding base or it is applied in the form of astable diazonium salt. This simple and well-known cheap process is opento a very serious disadvantage. The printing pastes containing thediazonium salts and a carbohydrate thickener tend to thin out rapidlylosing their desired printin consistency. It is with this thinningaction that Y the present invention is concerned. According tothepresent invention the diazonium salt is associated with a watersoluble suli'on'ic acid containing at least one oleflnic double bond oracetylenic triple bond for each '10 carbon atoms.

When an aromatic amine .solution, a diazonium salt is formed which isgenerallyassumed to have the iollowing formula:

. mi-xwhere Ar stands for the aromatic radical or the diazo componentand X stands'for the anion of the acid. These diazonium'salts are saltsof the very strong diazonium bases and the aqueous solutions containessentially the diazonium cations and the anions oi the acid used, asindicated by the formula. Some or thesediazoniu'm salts are diflicult toisolate because of their great solu-' bility. Others are not so solubleand can be easily isolated. Someare diflicult to handle after ratherstable and do not represent an explosive hazard. It is also known thatif the anion of the is-d'a'ot' ed in id I z m or diazoamino anddiazoimino compounds which acid X- is properly chosen, in almost allcases diazonium salts of lower solubility may be produced and thereforeisolated, and it is also known that many of these diazonium salts havelost their explosive character andcan be storedand handled in the drystatewithout' danger; this kind of diazonium salts is sometimes referredto .as stabilized diazonium salts. They comprise such compounds ascertain aromatic sul-' fonates, without olefinic double bonds,Iborofluorides;- and particularly salts of complex acids sometimesreferred to as double salts, the mostimportant of them being the doublesalts of diazonium chlorides and zinc chloride' which correspond to thei'ormula:

ArN V a m) -'(zncm= v V v .N a I It should be borne-in mind thatalsothese stabilized diazonium salts including the above mentioneddouble salts are true diazonium salts,

i. 'e., the aqueous solution contains the same diazonium cations as thesolution or any other diazonium salt derived from the same base. Thestabilized diazonium salts should not be confused with other kinds ofstabilized diazo compounds such as dia'zotates, also known asnitrosamines,

' are only stable and applied in alkaline medium,

' diafzo compounds are referred to in this applicawhile on the otherhand the diazoniuni salts are only stable applied in acid medium. Thepresent types-oi diazo compounds. Whenever stabilized tion this termshall be interpreted to includeex- -isolation because oi. theirexplosivity, others are clusively stabilized diazonium salts and not to7 include diazotates or diazoamino or diazoimino compounds; 1

While it is not-intended to limit the present invention to any theory ofaction, we believe that I, it is highly probable that lowering ofviscosity of printing gums is essentially caused by the diazonium'cation because the same kind of thing rsultsregardlessoitheanionotthediamiumsaltandeventhedoublesalboffliestablliaed'diasoniumsaltsdescribedaboveexertaslmilar -printingpasteisnotcriticai'so longasitis on the acid side, for the present invention doesnot dealwithanyother typeset pastes. Alkaline media, as is well-known,cause rearrangement or thediaaoniumsaltstodiasoemnpoundsoidifl'ermtstructurewhicharereferredto asdiaaotates ornitrosamines.

While not desiring to limit the invention thereto, we believe that theevidence strongly indicates thatthethinningactionisacolioidalphenmnenonrather than a chemical reaction. The following test was made: Adiazonium salt derived from z-nitro-i-methoxy aniline was added to aprinting paste made up with a starch thickener;aiterzohoursthethenwaterthinsolutionwas coupled with an alkalinesolution of betanap'nthol and. the sac dye formed was removed byfiltration. 'Ihe amount of am dyestuii obtained indicated that the bulkof the diazonium salt was lmdeeomposed and had acted while the filtratestill showed the reaction of starch and not the reactions of reducingsugars.

The thinning action diiiers widely and depends upon the structure' ofthe diam component the diasonium salt derives from. We have foundthatthosediazoniumsaltsthatareknowntobe very active couplers are alsothe worst thinners, while those that are slow in coupling generally thinto a much lesser degree. Though there is certainly some parallelism inthe coupling power and thinning action these two properties are notstrictly proportionate. The diaaonimn salts that derive fromnitroanilines are the worst thinners. Particularly those deriving from2,4-dinitro-6- chloroaniline, from 2-nitro-4-chloroaniline, from2-nitro-4-methoxy aniline, from 2-nitro-4- methylaniline thin thevegetable gums very badla'The diamnium salts deriving from o-nitranilinethin more than those deriving from the meta and para compounds. On theother hand the diazonium salts deriving from the2-methyl-4-chloroaniline and iron:- o-anisidine have only littlethinning action. Obviously, the rate of the thinning depends upon theconcentration oithe diasonium ions present in the printing paste- Thethinning action has been observed with all thickeners prepared frommaterials of vegetable origin such as starches, gums, alkyl celluloses.etc.

Wheat starch, corn starch, rice starch, sweet P- tato starch, tapiocastarch, chlorinated starch,

maybe mentioned as examples of starches. Carob bean mm and gumtragacanth may be mentioned as examples or gums and methylorethylceilulose as examples of allwl celluloses. Obviously, also mixturesof these materials are quite often used in thickeners and theirviscosity is e? influenced by dianonilmi salts. It will be no all ofthese thickeners are carbohydrates or carbohydrate derivatives. In theclaim the expremon carbohydrate thickener is used in a broad sense tocover pure carbohydrates and derivatives. j

The water soluble suiionic acids containing at least one olefinic doublebond or acetylenic triple bond for each 10 carbon atoms have the general'il operty of preventing or reducing the thinning action of diazoniumsalts cm printing pastes. The

deereasestheamnityofthediazonimncafionandinhibitsitsacflmupunthethickener. Whemthethickenerlaflrstaddedtothediamhnnsaltmlutioniollowedbyaddiiionotthethinninginhihitor,thinning is prewnted to ,a much lesse degree.Apparentlyinsuchacasethediamium salt has already commenced its thinningaction onthethickenerandtheactionisnotreversihlesothattheadditionofthethinninginhibitordoes notremedythedamagealreadydone.

The present invention includes all the dissoniuni salts derived fmm iceeolor'diam nmtathatistosamnomalldiazotizable aromatic aminesfreefromsolubilizinggroupsuseiulin makingiceeolorsoramicpigments. Typicalaretheiollowing:

Aniline and its homologues, as e. g. the toluidines,2,4-dimethylaniline; halogen derivatives of aniline andof itshomologues'.ase. g. the momfluomanilines, the monochloranilines,Zn-dimmroaniline, Z-fluoro-S-chloroanilhre, 25 4mmroanillne, maminobenzois'ifluoride, p-aminobensotrifluoride, 3 amino-4chlorobenzotrifiucide, 2-methyl-3-chloroaniline, 2-methyl-4-chlo- 4aroaniline, 2-methyl-5-chlornaniline, S-methwL i- 2-methoxy 5bromoanillne, 3-bro1no-6-ethoxyaniline, 4-ch1oro-2-amino-diphenylether,4-amino 2 chloro-diphenylether, i-amino-f-chlorodiphenylether, 4',4'-dichloro 2 amino diphene yletber,2,2,5'-trichloro-4-amino-diphenylether; ether derivatives of aniline andits homol es containing 'nitro groups as e. g. 2-methoxy-4-nitroaniline, 2-methoxy-5-nitroaniline, 2-nitro- 4-methoxyaniline,2-methoxy-4-nitro-'-5-methyl.- aniline; monoacyl derivatives of aromaticdiamines, as e. g. N-hexahydrobenzol-p-pheny1-. ene diamine;N-hexahydrobenzoyl-p-toluyh enediamine, N-benzoyl p phenylene diamine;monoacyl derivatives of diaminophenol ethers, as e. g.2-benzoy1aminof-4- amino-aniaole, 2

hexahydrob'enaoylamino 5 aminoanisole, 2 amino 5 benzoylaminohydroquinone dimethyl ether and diethylether, z-amino-d-hexahydroamition. Typ cal heterocyclicamines are 2-aminoycarbazole, 3,6diaminocarbazole, 2-nitro-3'-a-'- mino-carbazole, 2 nitro3'-aminodibenzofuran, Z-amino 3-nitrobenzothiophene, 1amino-5-fludiethylether, '2 amino 5 butyrylamino-hydroquinonedimethylether and diethylether, 2-amino- 5 phenoxyacetylamino-"hydroquinone diethylether, the ,monomethyl and the monobenzyl and themonophenyl-urethane of 2,5-diamino- 1 I benzoylamino-hydroquinonedimethylether andhydroquinone dimethylether and diethylether, 1-

amino-3-benzoylamino-4,6-dimethoxy benzene;

' analogous monoacyl derivatives of 2,5-diamino-4- alkoxy-toluenes andof 2,5-diamino 4-alkoxy chlorobenzene and of2,5-diamino-4-alkoxy-benzene sulfodialkylamides; analogous monoacylderivatives of 1,3-diamine-4,6-dimethylbenzene; the diethylamide f2-amino-4(4'-chlorophenoxy) -benzoic acid; monoacyl derivatives ofdiamino-p-chlorophenyl ethers as e. g. 2-amino-4- 'chloro-fi-acetylaminodiphenylether, 2-benzoylamino-4-chloro-5-aminoanisole; amino derivativesof aromatic sulfones as e. g. 3-amino-4- methy-diphenyl sulfone,2-amino-4'-methyl-diphenyl sulfone, 2-amino.-4-acetyl-diphenyl sul--fone, the ethyl ester of 3-amino-4-(p-toluene-- sulfonyl) -ben'zoicacid, 4 methoxy 3 aminophenyl ethyl sulfone, (4 methoxy. 3aminophenyD-benzyl sulfone, 4-ethoxy-3-amino-diphenyl sulfone, 2 amino 4(trifluoromethyl) phenyl-ethyl sulfone; amino derivatives ofaromethyl-benzene. dimethylsulfonamide and diethylsulfonamide, 3.-'amino'4 methoxy-benzene diethylsulfonamide; xenylamine; alpha and betanaphthylamine; alpha aminoanthraquinone; 2-

'amino-3-nitro-efluorene and 2-amino 3 nitro- .fluorenone;amino-diarylamines and their ether derivatives and their nitroderivatives as e. g- 2- methoxy-S-amino-diphenylamine, 4-methoxy-4-amino'diphenylamine, 4 ethoxy 4'-'a-mino-diphenylamine, 3,4'-dinitro 4amino-diphenylamine; aminp-azd' compounds, as e. g.3,2'-dimethyl-4-amino-azobenzene, 2-methyl-4-amino- 5methoxy-4'-chloroazobenzene,4-amino-4'-nitr0-3-methoxy-6-methyl-azobenzene, 4 amino'4'-nitro-2,5-dimethoxy-azobenzene, 4-amino-4'- chloro-3methoxy-6-methyl-azobenzene, the azo dye; diazotized o-anisidine coupledonto alpha naphthylamine.

include the water soluble sulfonic acids that contain at least oneoleflnicdouble bond or acetylenic triple bond. The inhibitors of thepresent invention may contain one or more oleflnic double bonds oracetylenic triple bonds in the same molecule, or they may contain bothdouble bonds and triple bonds, We have found that the anti-thinningaction appears to depend mainly on the presence of the double or triplebond. In, order to be practically efl'ective, we have found that theremust be a certain minimum number of the unsaturated bonds in a moleculeof given size.

.Practically useful anti-thinning action is obtained when there is atleast one double bond or triple bond per 10 carbon atoms of themolecule. of the sulfonic acid. The unsaturated bond may be locatedalmost anywhere in the molecule. Thus, it

. may be linked directly to the carbon to which the sulfonic acid groupis connected or it may be located elsewhere in a carbon chain, which maybe interrupted by other elements such as oxygen,

' matic dialkylsulfonamides as e. g. 3-amino-4- nitrogen, sulfur and thelike.

The sulionic acid compounds used in the present invention are truesulfonic acids or sulfonates, that is to say organic compoundscontaining the group EC-SO3H, and it is necessary that the inhibitor befree from groups which are capable of azoic coupling with the diazocompound or condensation to form a diazoamino or diazoimino compound inacid medium.- Itis also necessary that the cation of the inhibitor shallnot becapa- There are also diazonium salts derivin from aromaticdiamines in which only one of theamino groups is diazotized-and theyalso fall within the 1 scope of the present inventionz An example ofthis type of amine is 2,6-dichloro-1,4-phenylene diamine. Diazoniumsalts deriving from diamines in which both amino groups are diazotized-to form tetrazo compounds fall within-its scope. Typical amines of thisclass arep-phenylene diamine, benzedine, vo-tolidine, o-dianisidine,4,4- diamino stilbene, 4,4-diamino diphenylamine,

- '2,2'.-dimethyl-4,4'-diamino diphenylamineand 71,5-diaminonaphthalene.

Also di nium alts deriving from heterocyclic nmofiamines fall under thepresentinvenorobenzothiazole:

of difierent diazonium ble of coupling with the diazo compound,condensing therewith to form a diazoalnino or diazoimino body or ofcatalytically decomposing it. as is the case with certain coppercompounds.

The present invention is not limited to using a single inhibitor andmixtures are equally efiective.

Since the sulfonicacid compounds stabilize in an aqueous composition theacid itself or its water soluble salts may be used. I

Examples of aliphatic sulfonic acids containing one double bond are:ethylene sulfonicacid, 2- propene-l-sulfonlc acid, 2-methyl-2-propene 1-sulfonic acid, Z-butene-l-sulfonic acid,lgl-dimethyl-Z-propene-l-sulfonic acid, 3,3-diethyl-2- propenel-sulfonic acid. Examples ofaliphatic sulfonic acids containing twodouble bonds are:

1,6-heptadiene-4-sulfonic acid, 3,7-dimethyl 2,6-.

octadiene-l-sulfonic acid. As an example of an aliphatic sulfonic acidwith a triple bond there 7 1 may be mentioned 2-propine-l-sulfonic acid.

With the exception of ethylene sulfonic acid these aliphatic sulfonic'acids are most conveniently prepared by reactingthe correspondingchloride with sodium sulfite in the well-known manner.

The unsaturated grouping does not necessarily have to be connected to.the sulfonic group by a carbon chain. On. the contrary this chain may beinterrupted by other atoms. Typical examples are N -a'llyl taurine,diallyl suffosuccinate, and dimethallyl sulfosuccinate, a compoundcontaining 12 carbon atoms and two olefinic double bonds. tainedfromthe'corresponding maleic acid esters by reaction with sodium bisulilte.

The sulfonic acids of the present invention need not belong to thealiphatic series. On the contrary. they may contain ring systems, solong as there is at least one olefinic double-bond or a. triple bond. Itshould be noted that the double bond must be oleflnic in nature, thusfor example the double bonds in the benzene ring are not olefinic innature and accordingly benzene sulfonic acid does not behave as aninhibitor and is not included in the present invention. How- The lattertwo compounds may be 'ob- 4 ever, alicyclic compounds which do containdouble bonds of oleilnic character are active inhibitors. Typicalexamples are cyclohexene 3 sulionic acid, l-p-menthene-ii-sulfonic acidand 1-pmenthene-4-sulfonic acid which are obtainable in the moleculedoes not affect its inhibiting,

action provided that the molecule also contains olefinic double bonds oracetylenic triple bonds outside of the aromatic ring. Typical examplesof such compounds as styrene-beta-sulfonic acid, alpha metlmlstyrene psulfonic acid, phenyl acetylene-p-sulfonic acid, and the like.

As with the purely aliphatic compounds referred to above, the sulionicgroup does not, have to be connected to the unsaturated group through acarbon chain onlv. Thus for example the allyl ether of phenolp-suli'onic acid acts as inhibitor.

Heterocyclic sulfonic acids are also useable as long as they containdouble bonds or triple bonds of oleilnic or acetylenic characterrespectively. These bonds may be inside or outside of the heterocyclicngs.

Inhibitors of the present invention may have other substituent groups,thus for example allyl ethers of Z-sulfo-i-nitrophenol,2-sulio-4-chlorophenol, or 2-sulfo-4-aminophenol are useful inhibitors.

It should be noted however, that the inhibiting effectiveness is notimaifected by the presence of azotization. If the inhibitors are used inthis manner they obviously should not contain diazotizable amino groups.In the second place diazonium salts .either stable per se or stabilizedin a customary way, may be blended with the inhibitor to form solidcompositions suitable for incorporation into printing pastes. Theobvious equivalent is to add the inhibitor to a separately prepareddiazo solution before the printing paste is made up. It does not makeany difference what procedure is used in every case the thinning of Allsubstituents. The so-called negative substituents when attached directlyto a carbon of the double bond group lower the inhibiting action. Thusethylene sulfonic acid is by no means as powerim an inhibitor as 2propene 1 sulfonic acid where the negative group is separated from thedouble bond by a methylene group. This be havior appears to be generalwith the sulfonic acids of flue present invention and is furtherevidence that the double or triple bond is the portion of the moleculewhich apparently exerts the primary inhibiting Since the sullonic acidsof the present invention behave as they do by reason of their anion andtheir effectiveness is not greatly influenced y the nature of the cationexcept where it interferes as in the case of copper, it is preferable'inmany cases to use a salt of the. sulfonic acid instead of the sulfonicacid itself as these salts may be very readily handled.

The sodium and potassium salts of the sulfonic the printing gum isgreatly delayed.

If the diazonium salt is first mixed with the printing gum and theinhibitor is added afterwards, then in a great many cases of very activeI diazo compounds a certain amount of thinning has already taken placebefore the inhibitor is added. This procedure, therefore, should be usedonly where the thinning action is slow, but it is included in the broadscope of the invention.

The invention will be further illustrated with the specific exampleswhich describe typical embodiments of the present invention. The partsare by weight;

Example 1 Four parts of a mixture of the zinc chloride .double salt ofthe diazonium chloride obtained cH2='cH cHiso3Na are dissolved in 21parts of water and the resulting solution is thoroughly mixed with '75parts of a 2 /2% carob bean" gum. The resulting paste is suitable foruse in the production of fast color prints on textile material,especially cotton cloth,

acids oi the present invention are the cheapest nes and in general themost convenient to prepare. The invention, however, is not in any senselimited to the use of these preferred salts and on the contrary othersalts such as zinc or calcium salts may be used. Ammonium salts andsalts of organic bases such as amines, amidines. guanidines and thelikemaybeused.

The inhibitors of the present invention may be added intwo stages.either before or after the dimotization. In the first place the aromaticbases known as ice color diazo components may be blended with theinhibitor and such blends maybe subsequently diaaotired in the customarymanner and incorporated into a printing paste.

, The equivalent of this procedure is to dissolve the impregnated withice color coupling components such as the anilide of 2-hydroxy-3-naphthoic acid, bis-acetoacetic-o# t0lidide, etc. Theadvantage of a printing paste such as this over one made in a similarmanner, but without the-sulfonate is shown in the following table:

The relative viscosity is expressed by the times in seconds taken forcopper plated steel shot weighing approximately 0.107 gram each to fallthrough millimeters of the printing paste.

Example 2 In a manner similar to that described in Example 1 printingpastes are made containing the zinc chloride double salts of thediazonium chlorides of the following ice color bases, sodium-2-methyl-2-propene sulfonate of the following formula:

', cu,=c--on,-soma and suitable thickening gums. In every case thesulfonate inhibits the thinning of the printing paste as is shown in thefollowing table:

. a 5 ice color coupling components. The superiority .oi a printingpaste thus made over one similarly Stabilized Parts real I I v ViscosityTime of Method oi Base used for the Diluent of SW i f Water Kind andpercent measuresecond g g ig measurepreparation of ,bmzed sponds topropene used, oi gum used (75 ment 2 reading measure}: ment of discoputs real Sultanate parts parts) 7 min. alter alter went relative mm 1mixing mixing viscosity Hours 3-nitro-4-amino. Magnesium 0. 74 0.106 21Carob bean 2.5%-. 79.6v 2 34.3 A1 nfiia'r'aaira' o 3'52 8106 2-2 3 3 iio 0. s4 0 46.0 s 15. 4 A1 0. 81 I 0. 106 56. 6 3 37. 7 A1 0 0.81 0 21-....do 53.6 .3 6.0 A1 3-nitro-4-amino 0.84 0. 273 21 Methyl cellulose40. 6 21 23. 4 1 A3 anisole. gi iethocel 4000) m o 0.84 o 21 .....?1'040.5 21 7.2 113 Dianisidin 0 0. 61 0. 106 21 Carob been 2 l9. 3 2 13. 6A2 Dn o 0.61 0 21 --.-do 20.0 2 6.3 A2

1 Nora-0n viscosi y u e t Al Cu lp Steel shot weighing 8 g. dropped 130mm., time in seconds. A2 Cu plated steel shot weighing .107 g. dropped130 mm., time in sccon' s. A3 glass spherical beads .097 g. dropped 130mm.,- time in seconds.

Example 3 An intimate mixture is made of 100 parts of 3- nitro-4-aminoanisole, 25 parts of sodium-2- methyl-2-propenevl-sulionate ofapproximately 73% purity, and 75 grams of sodium chloride. This mixturecan be treated with mineral acid and sodium nitrite and the resultingdiazo solution can then be bufiered .with sodium acetate and mixed withthickening gum for the production of fast color prints on textilematerials'impregnated with ice color coupling components such asarylides of 2-hydroxy-3-naphthoic acid, etc.

Printing pastes made from such mixtures have "the advantage overthosepastes made from the prepared but without the sulfonate is shown bythe following figures:

The viscosity measurements indicated above are the times in seconds forlead shot weighing advantage can best be seen by consulting the fol- 3lowing table. In this table the change of viscosity 0.069 gram each tofall 130 millimeters.

Example 5' 5.03 parts of the zinc chloride double salt obtained fromdiazotized 3-nitro-4-amino anisole corresponding to 16.7% real base aremixed with 0.408'part or the allyl ether of sodium p-phenol sulfonate.This mixture is dissolved in 21 partsof water and the resulting solutionis intimately. mixed with 75 parts of 2.5% carolo bean gum. incsuperiority of a printing paste thus made chloride double salt obtainedfrom tetrazotized o-dianisidine corresponding to 48.8% of real base and0.215. part of potassium 2-methyl-2-pro-' pene-1.-sulfonate of 70%purity are intimately mixed and dissolved in 23 parts of water and v theresulting solution is thoroughly mixed with 75 parts of 2% carob beangum. This viscous paste I. 1 V J 158g parts of a product containing thezinc is useful fort e preparation of deep blue patterns upon ce lulosicmaterial impregnated with I) arylides of 2-hydroxy-3-naphthoic acid, orother 76 weighing 0 10? gram each to fall 130 millimeters.

P8118 0f 73 Tim f I Ziggy Part5 z cjf i' i l g if Second Inert diluentand real parts) gum v cos yviscosit v cos y 3- diam'iud f' ggi'g partsper part base base in used and strengt jgfgff reading f ggz mixing f IHours 5-nit c-2-amino anisole 8.5 Sodium chloride 0.3 OargEBean 2.5%-. 212.3

o------ l 4-chloro2nitro-aniline. 0. 0 0, 9 .do 27.0 4 13.5 A2; Do 9 o0.69 -do 24.1 4 0.8 A2

*' Emmple 4 over one similarly prepared, but without inhibitor is shownin the following -table:.

Relative Relative viscosity viscosity Printing paste used measurementmeasurement after 5 alter 4 minutes hours Paste containing inhibitor..-60. 2 29. 8 Paste without inhibitor- 47. 0 0. 7

These relative viscosity measurements are the times in seconds forcopper plated steel shot 6* moans 1 Brande?- with '15 ports of 25%carol! gum. The actw sulfonicacidcompmmdbcingmcimttosoblhniiam' inhibitthinning of the carbohydrate 3. lcompositionaccordingtoclann linwhichthe diazonium salt is a diazonium chloride-zinc chloride double salt.

4. A composition according to claim 2 in which the is a diazoniumchloride-zinc chloride double salt.

A composition comprising a water solvanfiage: of'the printing paste thusprepared over me H mm salt derived from 34] I onemade but without theinhibitor is shown in the following: table:

g who Relative Printfiigposteused 1! m2 ms minutes: hum

Paste: confirming; inhihitor..- Pal 43.4 Pastewiihoutinhibitor..- 141.3;I

These relative. viscosity measurements are the times in seconds forspherical glass beads weighing 0.0% gram to: 1301 mm'irneiers;

can be seen styrene: beta-sulionaie' is a, less efl'ecti ve inhibitorbecause: of the proof-mil oi the double bond and of the group.

application is in part; a. oi

our; co-pending application, Serial No. 431,224,,

l1. Diazo compositions suitable for printing, containing e water solublesalt defroxn an ice color diam component and an organic compound notmore than 11 carbon atoms: belonging to group consisting oi watersoluble acids containing at East one oleflnicdouble bond for eachlflcarbonatomo, water soluble acids containhlg at least one acetglenicbond. for 10 carbon atoms, and water soluble salts. or the above acids,the sultonic acid compounds being free from constituenis capable of uoiccoupling with the disalt, catalytic decomposition thereof at roomtemperature or therewith to form diazoamino or diazoimino compounds inacidmediunu-theamouncotthesulionicacidl pound being suilicient 'tosubstantially inhibit thinning of a carbohydrate 2, A paste acarbohydrate thickener atleast one soluble dluonium'salflderired-firomanicecolordiamcompcncntandmorganiocompolmdhavingnotmorethanmcarbonaiomsbelonging-tothcgroupcmslsiingernmmmmemumwwumnmmuleastoueoleflnicdoublebondioc 10 carbonaboms,

ntersoluble sulfonic acids containing at leastmaceiylenictriplebmaifcreaohlllcarbcnmandwatcrsohxblesalisottheaboreacids.

ibcsulionicacidcmnpoundbeing'frccfromconsfimentscapoblcotamiccmlplingwiththe dicanpotmdr anisole and a suihcient amount of sodium2- mefihwl-E-propene-i-sulfonate \to substantially inhibit of a.carbohydrate printing thickener by the diazonium salt.

6 A priniing paste containing a carbohydrate thickener and awatersoluble diazonium salt derived from diazotized 3-nin'o-4-amino-aniso1cand & sufioiem"r amount of sodium 2-methyl-2- m a mopene-l-sulfonatc tosubstantially inhibit thinning of the paste.

T. A composition suitable for the preparation of printing pastescontaining carbohydrate gum comprising an" ice color fonm'mg componencincluded in the group consisting of compositions containing watersoluble diazonium salts and intermediates therefor consisfing of aminesdiazotizablc to produce compositions containing water soluble diazoniumsalts, the color forming w component having associated therewith anorganic compound with not more than 12 carbon atoms selected from thegroup consisting or water soluble sulfonic acids containing at least oneolefinic double bond for each 10 carbon atoms,

a; water solublesulfonic at least one acetylenic triple bond for each 10carbon atoms, unclv water soluble salts of the above acids, the sulfonicacid compounds being free from constituents capable of azoic couplingwith the disalt, catalytic dccompodtion thereof at room temperamre, orcondensation therewith to formdiazoaminoordiazoiminocompolmdsin acidmedium, the amount. of sulfonic acid compound being surlficient tosubstantially inhibit 45 thinning of a carbohydrate thickener.

8. Acompodtion accordingtoclaim'l inwhich thethinninginhibitoristhesodumsaltof Z-methxl-Z-propene-l-sulfonic acid.

' 0. A composiiion according to'claim 1 in which SG-the thinninginhibitor is the sodium salt of 2-methu1l-2-propene-1-sulfonic acid.

ma composition according to claim 3 in which. the thinning inhibitor is2-metbyl-2- m which the thinning inhibitor B,H-a.'fly1 taurine.

'mmsnmcnen.

